EP2666825A1 - Resin composition, and printed wiring board, laminated sheet, and prepreg using same - Google Patents

Resin composition, and printed wiring board, laminated sheet, and prepreg using same Download PDF

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Publication number
EP2666825A1
EP2666825A1 EP12736878.5A EP12736878A EP2666825A1 EP 2666825 A1 EP2666825 A1 EP 2666825A1 EP 12736878 A EP12736878 A EP 12736878A EP 2666825 A1 EP2666825 A1 EP 2666825A1
Authority
EP
European Patent Office
Prior art keywords
group
resin composition
composition according
resin
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12736878.5A
Other languages
German (de)
French (fr)
Inventor
Masato Miyatake
Tomohiko Kotake
Shunsuke NAGAI
Shintaro Hashimoto
Yasuo Inoue
Shin Takanezawa
Hikari Murai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of EP2666825A1 publication Critical patent/EP2666825A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C—CHEMISTRY; METALLURGY
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    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C—CHEMISTRY; METALLURGY
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C—CHEMISTRY; METALLURGY
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2203/20—Applications use in electrical or conductive gadgets
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important

Definitions

  • the present invention relates to a resin composition having insulating properties, heat resistance, and the like and also having especially excellent low thermal expansion properties, which is used for electronic components and so on, and to a prepreg using the same, a laminate, and a printed wiring board.
  • a laminate for printed wiring board is generally formed by curing and integrally molding a resin composition containing an epoxy resin as a major ingredient with a glass woven fabric.
  • the epoxy resin is excellent in a balance among insulating properties, heat resistance, costs and the like.
  • the epoxy resin has a large coefficient of thermal expansion, it is attempted to reduce the thermal expansion by selecting an epoxy resin having an aromatic ring or filling an inorganic filler such as silica in a high density (see, for example, Patent Document 1).
  • a polybismaleimide resin which is widely used for high-density mounting or highly multi-layered laminate is very excellent in the heat resistance, it has high moisture absorption and a problem with the adhesion. Furthermore, as compared with an epoxy resin, the polybismaleimide resin requires a high temperature and a long time at the time of lamination, so that it has a drawback that the productivity is poor. That is, in the case of the epoxy resin, it can be generally cured at a temperature of 180 °C or less, whereas in the case of laminating the polybismaleimide resin, a long-term treatment at a high temperature of 220 °C or higher is required.
  • a modified imide resin composition is improved in moisture resistance and adhesion (see, for example, Patent Document 2); however, since it is modified with a low-molecular weight compound containing a hydroxyl group and an epoxy group for the purpose of ensuring solubility in commonly-used solvent such as methyl ethyl ketone, the resulting modified imide resin is significantly inferior in the heat resistance to the polybismaleimide resin.
  • an object of the present invention is to provide a resin composition which is especially excellent in heat resistance and low thermal expansion properties, and a prepreg using the same, a laminate and a printed wiring board.
  • the present invention provides a resin composition, a prepreg, a laminate, and a printed wiring board as described below.
  • each of R 3 and R 4 independently represents an alkyl group, a phenyl group, or a substituted phenyl group; and n represents an integer of 1 to 100;
  • each of R 6 , R 7 , R 8 , and R 9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and D represents an alkylene group or an aromatic hydrocarbon group,
  • each of R 6 , R 7 , R 8 , and R 9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and B represents single bond or any one of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group;
  • a prepreg obtained by impregnating or coating a substrate with a resin composition of the present invention, a laminate manufactured by laminating and molding the prepreg, and a multilayer printed wiring board manufactured by using the laminate are excellent in glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics, and are useful as a printed wiring boar for electronic devices.
  • the present invention is described in detail below.
  • the present invention is concerned with a resin composition
  • a resin composition comprising (a) a maleimide compound having at least two N-substituted maleimide groups in a molecular structure thereof and (b) a silicone compound having at least one reactive organic group in a molecular structure.
  • maleimide compound having at least two N-substituted maleimide groups in a molecule as the component (a) in the resin composition of the present invention examples include N,N'-ethylenebismaleimide , N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidopheny
  • maleimide compounds bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, N,N'-(1,3-phenylene)bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, and polyphenylmethane maleimide are preferred from the viewpoint of high reactivity and higher heat resistance; and bis(4-maleimidophenyl)methane is especially preferred from the viewpoint of solubility in a solvent.
  • silicone compound having at least one reactive organic group in a molecular structure as the component (B) examples include a silicone compound containing a structure represented by the following general formula (II):
  • each of R 3 and R 4 independently represents an alkyl group, a phenyl group, or a substituted phenyl group; and n represents an integer of 1 to 100.
  • a silicone compound having at least two reactive organic groups in a molecular structure is suitably used as the component (b) ; and a silicone compound having reactive organic groups on both ends of the above silicone structure, a silicone compound having a reactive organic group on either end, a silicone compound having a reactive organic group in the side chain, and a silicone compound having a reactive organic group in the side chain and on at least one end are used.
  • Examples of the reactive organic group in the silicone compound having at least one reactive organic group in a molecular structure of the component (B) include an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group.
  • the silicone compound having an epoxy group or epoxy groups in a molecular structure commercially available products can be used.
  • Examples thereof include products having epoxy groups on both ends, such as “X-22-163” (functional group equivalent weight: 200), “KF-105" (functional group equivalent weight: 490), “X-22-163A” (functional group equivalent weight: 1,000), “X-22-163B” (functional group equivalent weight: 1,750), and “X-22-163C” (functional group equivalent weight: 2,700); products having alicyclic epoxy groups on both ends, such as “X-22-169AS” (functional group equivalent weight: 500) and “X-22-169B” (functional group equivalent weight: 1,700); products having an epoxy group on either end, such as “X-22-1730X” (functional group equivalent weight 4,500); products having epoxy groups in the side chain and on both ends, such as “X-22-9002" (functional group equivalent weight: 5, 000) ; products having an epoxy group in the side chain, such as “X-22-343” (functional group equivalent weight: 525), “KF-101” (functional group equivalent weight: 350), “KF-1001” (functional group equivalent weight: 3,500), "X-22-
  • silicone compounds having an epoxy group or epoxy groups in a molecular structure are preferred from the viewpoint of heat resistance, "X-22-163A” and “X-22-163B” are more preferred; and "X-22-163B” is especially preferred from the viewpoint of low coefficient of thermal expansion.
  • silicone compound having an amino group or amino groups in a molecular structure commercially available products can be used.
  • examples thereof include products having amino groups on both ends, such as "KF-8010" (functional group equivalent weight: 430), “X-22-161A” (functional group equivalent weight: 800), “X-22-161B” (functional group equivalent weight: 1,500), “KF-8012” (functional group equivalent weight: 2,200), “KF-8008” (functional group equivalent weight: 5,700), “X-22-9409” (functional group equivalent weight: 700), and “X-22-1660B-3” (functional group equivalent weight:2,200), all of which are manufactured by Shin-Etsu Chemical Co., Ltd., and "BY-16-853U” (functional group equivalent weight:460), “BY-16-853” (functional group equivalent weight: 650), and “BY-16-853B” (functional group equivalent weight: 2,200), all of which are manufactured by Dow Corning Toray Co., Ltd.; and products having an amino group in the side chain, such as "KF
  • silicone compounds having an amino group or amino groups in a molecular structure X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and BY-16-853B are preferred from the viewpoint of low coefficient of water absorption; and X-22-161A, X-22-161B, and KF-8012 are especially preferred from the viewpoint of low thermal expansion properties.
  • silicone compound having a hydroxyl group or hydroxyl groups in a molecular structure commercially available products can be used. Examples thereof include products having hydroxyl groups on both ends, such as “KF-6001” (functional group equivalent weight: 900) and “KF-6002” (functional group equivalent weight: 1,600), all of which are manufactured by Shin-Etsu Chemical Co., Ltd.; products having phenolic hydroxyl groups on both ends, such as “X-22-1821” (functional group equivalent weight: 1,470), manufactured by Shin-Etsu Chemical Co., Ltd., and “BY-16-752A” (functional group equivalent weight: 1,500), manufactured by Dow Corning Toray Co., Ltd.; products having a hydroxyl group on either end, such as “X-22-170BX” (functional group equivalent weight: 2, 800) and “X-22-170DX” (functional group equivalent weight: 4,670), all of which are manufactured by Shin-Etsu Chemical Co., Ltd.
  • products having a hydroxyl group in the side chain such as “X-22-4039” (functional group equivalent weight: 970) and “X-22-4015” (functional group equivalent weight: 1,870), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • silicone compound having a methacryl group or methacryl groups in a molecular structure commercially available products can be used. Examples thereof include products having methacryl groups on both ends, such as “X-22-164A” (functional group equivalent weight: 860) and “X-22-164B” (functional group equivalent weight: 1,630); and products having a methacryl group on either end, such as "X-22-174DX” (functional group equivalent weight: 4,600), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • silicone compound having a mercapto group or mercapto groups in a molecular structure commercially available products can be used. Examples thereof include products having mercapto groups on both ends, such as “X-22-167B” (functional group equivalent weight: 1,670); and products having a mercapto group in the side chain, such as "KF-2001” (functional group equivalent weight: 1,900) and “KF-2004” (functional group equivalent weight: 30,000), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • silicone compound having a carboxyl group or carboxyl groups in a molecular structure commercially available products can be used. Examples thereof include products having carboxyl groups on both ends, such as "X-22-162C” (functional group equivalent weight: 2,300); products having a carboxyl group on either end, such as “X-22-3710” (functional group equivalent weight: 1,450); and products having a carboxyl group in the side chain, such as "X-22-3701E” (functional group equivalent weight: 4,000), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or by mixing two or more thereof.
  • silicone compound having an alkoxy group or alkoxy groups in a molecular structure commercially available products can be used.
  • examples thereof include products having an alkoxy group in the side chain, such as "FZ-3704" (functional group equivalent weight: 150), which is manufactured by Dow Corning Toray Co., Ltd. These may be used alone or by mixing two or more thereof.
  • the used amount of the component (b) is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass based on 100 parts by mass of the component (a).
  • the used amount of the component (b) is 1 part by mass or more, it is possible to realize a low coefficient of thermal expansion.
  • the used amount of the component (b) is 100 parts by mass or less, adhesion to a copper foil and moldability can be ensured.
  • the resin composition of the present invention further comprises (c) a thermosetting resin.
  • a thermosetting resin as the component (c) is not particularly limited, examples thereof include an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, and a melamine resin. These may be used alone or by mixing two or more thereof. Among them, an epoxy resin and a cyanate resin are preferred from the viewpoint of moldability and electric insulating properties.
  • the epoxy resin examples include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, a bisphenol F novolac type epoxy resin, a stilbene type epoxy resin, a triazine skeleton-containing epoxy resin, a fluorene skeleton-containing epoxy resin, a triphenolphenolmethane type epoxy resin, a biphenyl type epoxy resin, a xylylene type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, a diglycidyl ether compound of a polyfunctional phenol compound or a polycyclic aromatic compound such as anthracene and a phosphorus-containing epoxy resin having a phosphorus compound introduced thereto.
  • These may be
  • the cyanate resin examples include a bisphenol type cyanate resin such as a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate resin; and a prepolymer thereof which is partially converted into triazine. These may be used alone or by mixing two or more thereof. Among them, a novolac type cyanate resin is preferred from the viewpoint of heat resistance and flame retardancy.
  • the used amount of the component (c) is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass based on 100 parts by mass of the component (a).
  • the used amount of the component (c) is 10 parts by mass or more, more excellent moisture absorption characteristics and adhesion to a copper foil are obtained.
  • the used amount of the component (c) is 200 parts by mass or less, heat resistance can be ensured, and it is possible to realize a low coefficient of thermal expansion.
  • the resin composition of the present invention further comprises, as a component (d), an amine compound having an acidic substituent represented by the following general formula (I).
  • Examples of the amine compound as the component (d) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline.
  • m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and synthetic yield; and m-aminophenol and p-aminophenol are more preferred from the viewpoint of heat resistance.
  • the used amount of the component (d) is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass based on 100 parts by mass of the component (a).
  • the used amount of the component (d) is 0.1 parts by mass or more, more excellent heat resistance and adhesion to a copper foil are obtained.
  • the used amount of the component (d) is 20 parts by mass or less, heat resistance can be ensured.
  • the organic solvent which is used for this reaction is not particularly limited, examples thereof include an alcohol based solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; an ether based solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene, and mesitylene; a nitrogen atom-containing solvent such as methylformamide, dimethylacetamide, and N-methylpyrrolidone; and a sulfur atom-containing solvent such as dimethyl sulfoxide.
  • an alcohol based solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • a ketone based solvent
  • cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferred from the viewpoint of solubility; cyclohexanone and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity; and propylene glycol monomethyl ether is especially preferred in view of the fact that it has a high volatility and hardly remains as a residual solvent at the time of manufacturing a prepreg.
  • a reaction catalyst for the above reaction may be used, and not particularly limited.
  • the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methyl imidazole and phenyl imidazole; and a phosphorus based catalyst such as triphenyl phosphine. These can be used alone or by mixing two or more thereof.
  • a reaction temperature is preferably 70 to 150 °C, and more preferably 100 to 130 °C.
  • a reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • a curing accelerator for the purpose of enhancing heat resistance, flame retardancy, adhesion to a copper foil, and the like, it is desirable to use (e) a curing accelerator in the resin composition of the present invention, and examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines, a quaternary ammonium salt. Among them, imidazoles and derivatives thereof are preferred from the viewpoint of heat resistance, flame retardancy, adhesion to a copper foil, and the like.
  • an isocyanate resin represented by the following general formula (III), or a compound substituted with a compound represented by the following general formula (IV), in which an imidazole group is substituted with an epoxy resin is more preferred because of excellent moldability at a relatively low temperature as not higher than 200 °C and excellent long-term stability of a varnish or a prepreg.
  • a compound represented by the following formula (V) or (VI) is especially preferred because it may be used in a small blending amount and is commercially inexpensive.
  • each of R 6 , R 7 , R 8 , and R 9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and D represents an alkylene group or an aromatic hydrocarbon group.
  • each of R 6 , R 7 , R 8 , and R 9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and B represents any one of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group.
  • the used amount of the curing accelerator (e) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and especially preferably 0.1 to 1 part by mass based on 100 parts by mass of the total amount of the components (a) to (d) in terms of solid content.
  • the used amount of the curing accelerator is 0.1 parts by mass or more, excellent heat resistance, flame retardancy and adhesion to a copper foil are obtained.
  • it is 10 parts by mass or less, the heat resistance, long-term stability and press moldability are not lowered.
  • the resin composition of the present invention may optionally comprise (f) an inorganic filler in combination.
  • the inorganic filler include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, a glass powder of E-glass, T-glass, D-glass, etc., and a hollow glass bead. These can be used alone or by mixing two or more thereof.
  • silica is especially preferred from the viewpoint of dielectric characteristics, heat resistance, and low thermal expansion properties.
  • examples of the silica include precipitated silica which is manufactured by a wet process and has a high water content; and dry process silica which is manufactured by a dry process and does not substantially contain bonding water.
  • the dry process silica includes crushed silica, fumed silica, and spherical fused silica depending on a difference of the manufacturing method. Among them, spherical fused silica is preferred from the viewpoint of low thermal expansion properties and high fluidity on being filled in the resin.
  • its average particle size is preferably 0.1 to 10 ⁇ m, and more preferably 0.3 to 8 ⁇ m.
  • the average particle size of the spherical fused silica is 0.1 ⁇ m or more, the fluidity on being highly-filled in the resin can be kept favorable.
  • it is 10 ⁇ m or less, an incorporation probability of coarse particles is reduced so as to suppress the generation of failure to be caused due to the coarse particles.
  • the average particle size as referred to herein means a particle size which is read off the cumulative distribution curve at the 50% point, with the total volume of particles being 100%, and it can be measured by a laser diffraction-scattering type particle size distribution analyzer and so on.
  • a content of the inorganic filler (f) is preferably 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass based on 100 parts by mass of the total components (a) to (d) in terms of solid content.
  • the content of the inorganic filler falls within the range of 10 to 300 parts by mass based on 100 parts by mass of the total resin components, the moldability and low thermal expansion properties of the resin composition can be kept favorable.
  • thermoplastic resin examples include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, a polyphenylene ether resin, a phenoxy resin, a polycarbonate resin, a polyester resin, a polyamide resin, a polyimide resin, a xylene resin, a petroleum resin, and a silicone resin.
  • Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.
  • Examples of the organic filler include a silicone powder, an organic material powder of tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether and so on.
  • an ultraviolet ray absorber such as a benzotriazole based material
  • an antioxidant such as a hindered phenol antioxidant and styrenated phenol
  • a photopolymerization initiator such as benzophenones, benzyl ketals, and thioxanthone-based type
  • a fluorescent brightener such as a stilbene derivative
  • an adhesion improver such as a urea compound such as urea silane and a silane coupling agent
  • the resin composition of the present invention is used as a varnish at the time of manufacturing a prepreg.
  • the solvent which is used for varnish is the same as the solvent which is used for the above reaction. It is preferred to use the varnish in a solid content concentration of 50 to 75 % by mass.
  • the prepreg of the present invention is obtained by impregnating or coating a substrate with the above-described resin composition of the present invention.
  • the prepreg of the present invention is described in detail below.
  • the prepreg of the present invention can be manufactured by impregnating or coating a substrate with the resin composition of the present invention, followed by semi-curing (B-staging) by heating for example.
  • As the substrate herein well-known materials which are used for various laminates for electrical insulating materials can be used. Examples of the material include fibers of an inorganic material such as E-glass, D-glass, S-glass, and Q-glass; fibers of an organic material such as polyimide, polyester, and polytetrafluoroethylene; and mixtures thereof.
  • such a substrate has a form, such as a woven fabric, a unwoven fabric, a roving, a chopped strand mat, and a surfacing mat
  • the material and the shape are selected depending on an application or a performance of the target molded article, and the material and the shape can be employed alone or in combination with two or more thereof, where necessary.
  • the substrate is not particularly limited with respect to its thickness, for example, those having a thickness of about 0.03 to 0.5 mm can be used.
  • Those having been subjected to a surface treatment with a silane coupling agent, etc., or those having been subjected to a mechanical opening treatment are suitable from the relievepoint of heat resistance, moisture resistance, and processability.
  • the prepreg of the present invention can be obtained by impregnating or coating the substrate with the resin composition in such a manner that an adhesion amount thereof to the substrate is 20 to 90 % by mass in terms of a resin content of the prepreg after drying, and then heating for drying usually at a temperature of 100 to 200 °C for 1 to 30 minutes to achieve semi-curing (B-staging).
  • the laminate plate of the present invention can be formed by laminating and molding the above prepreg of the present invention.
  • the laminate can be, for example, manufactured by such that 1 to 20 sheets of the prepreg of the present invention are superimposed, and a metal foil such as copper and aluminum is disposed on one surface or both surfaces thereof.
  • the metal foil is not particularly limited so far as it is used for an application of electrical insulating materials.
  • a molding condition for example, methods for a laminate and a multilayered board for electrical insulating material can be applied.
  • the molding can be performed within the temperature range of 100 to 250 °C under a pressure of 0.2 to 10 MPa for a heating time of 0.1 to 5 hours by using a multiplaten press, a multiplaten vacuum press, a continuous molding machine, or an autoclave molding machine, for example.
  • a laminate can be manufactured by combining the prepreg of the present invention with a wiring board for inner layer and laminating and molding the combination.
  • the printed wiring board of the present invention is manufactured by forming a circuit on the surface of the laminate. That is, a conductor layer of the laminate according to the present invention is subjected to wiring processing by a usual etching method, and a plurality of the laminates having been subjected to wiring processing are laminated via the above prepreg and then subjected to heat press processing, thereby achieving multilayering in block. Thereafter, a multilayered printed wiring board can be manufactured through the formation of a through-hole or a blind via hole by means of drill processing or laser processing and the formation of an interlayer connection by plating or with an electrically conductive paste.
  • Components (a) to (d), (e) a curing accelerator, and (f) an inorganic filler as shown below were mixed in a blending proportion (parts by mass) shown in each of Tables 1 to 5, and methyl ethyl ketone is used as a dilution solvent, thereby obtaining a homogenous varnish having a resin content of 65 % by mass. Subsequently, the above varnish was applied onto an E-glass cloth having a thickness of 0.1 mm, and heat-dried at 160 °C for 10 minutes, thereby obtaining a prepreg having a resin content of 50% by mass.
  • Example 1 Example 2
  • Example 3 Example 4
  • Thermosetting composition (parts by mass) (a) Maleimide compound Bis(4-maleimidophenyl)methane 40 40 40 40 40 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide (b) Silicone compound X-22-161A 15 15 X-22-161B 15 15 KF-8012 15 (c) Thermosetting resin Biphenyl aralkyl type epoxy resin 40 40 40 40 40 40 40 Bisphenol A type cyanate resin (d) Amine compound m-Aminophenol 5 5 5 p-Aminophenol 5 5 Curing accelerator G-8009L 0.5 0.5 0.5 0.5 0.5 (e) Inorganic filler Fused silica 50 50 50 50 50 50 Performances of laminate (1) Glass transition temperature (°C) 260 260 265 260 265 (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.5 9.0 8.5 9.0 (3) Solder
  • Example 10 Thermosetting composition (parts by mass) (a) Maleimide compound Bis(4-maleimidophenyl)methane 40 40 40 40 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide 40 (b) Silicone compound X-22-161A 15 15 15 X-22-161B 15 15 KF-8012 (c) Thermosetting resin Biphenyl aralkyl type epoxy resin Bisphenol A type cyanate resin 40 40 40 40 40 (d) Amine compound m-Aminophenol 5 5 5 5 p-Aminophenol 5 5 Curing accelerator G-8009L 0.5 0.5 0.5 0.5 0.5 (e) Inorganic filler Fused silica 50 50 50 50 50 50 Performances of laminate (1) Glass transition temperature (°C) 250 250 250 250 250 250 255 (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.0 8.5 8.0 8.5 (3) Solder dip resistance good good good good good good good good good good good
  • Example 11 Example 12
  • Example 13 Example 14
  • Thermosetting composition (parts by mass) (a) Maleimide compound Bis(4-maleimidophenyl)methane 40 40 40 40 40 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide (b) Silicone compound KF-864 15 X-22-163B 15 KF-6002 15 X-22-1821 15 X-22-164A 15 (c) Thermosetting resin Biphenyl aralkyl type epoxy resin Bisphenol A type cyanate resin 40 40 40 40 (d) Amine compound m-Aminophenol p-Aminophenol 5 5 5 5 5 5 5 5 Curing accelerator G-8009L 0.5 0.5 0.5 0.5 (e) Inorganic filler Fused silica 50 50 50 50 50 50 Performances of laminate (1) Glass transition temperature (°C) 260 260 260 260 260 (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.0 8.5
  • Example 18 Thermosetting composition (parts by mass) (a) Maleimide compound Bis(4-maleimidophenyl)methane 40 40 40 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide (b) Silicone compound X-22-167B 15 X-22-162C 15 FZ-3704 15 (c) Thermosetting resin Biphenyl aralkyl type epoxy resin Bisphenol A type cyanate resin 40 40 40 (d) Amine compound m-Aminophenol p-Aminophenol 5 5 5 5 5 Curing accelerator G-8009L 0.5 0.5 0.5 (e) Inorganic filler Fused silica 50 50 50 50 Performances of laminate (1) Glass transition temperature (°C) 260 260 260 (2) Coefficient of thermal expansion (ppm/°C) 8.0 8.5 9.5 (3) Solder dip resistance good good good (4) Warpage amount ( ⁇ m) 45 40 50
  • the Examples of the present invention are excellent in the glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics.
  • the Comparative Examples are inferior in any one of the glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics to the Examples.
  • a multi-layered printed wiring board manufactured by using a laminate which is manufactured by laminating and molding a prepreg obtained from the thermosetting resin composition of the present invention is excellent in glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics, and is useful as a highly integrated printed wiring board for electronic devices.

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Abstract

Disclosed are a resin composition containing (a) a maleimide compound having at least two N-substituted maleimide groups in a molecular structure and (b) a silicone compound having at least one reactive organic group in a molecular structure thereof; and a prepreg using the same, a laminate, and a printed wiring board.
A resin composition having excellent heat resistance and low thermal expansion properties; and a prepreg, a laminate, and a printed wiring board using the same can be provided.

Description

    [Technical Field]
  • The present invention relates to a resin composition having insulating properties, heat resistance, and the like and also having especially excellent low thermal expansion properties, which is used for electronic components and so on, and to a prepreg using the same, a laminate, and a printed wiring board.
    • [Background Art]
  • Associated with a trend toward miniaturization and high performance of electronic devices in recent years, in printed wiring boards, density growth and high integration of the wiring density is developed. Along with this, there is an increased demand for enhancement of reliability by increasing the heat resistance of laminates for wiring. In such an application, it is demanded to have an excellent heat resistance and also a low coefficient of thermal expansion.
  • A laminate for printed wiring board is generally formed by curing and integrally molding a resin composition containing an epoxy resin as a major ingredient with a glass woven fabric. In general, the epoxy resin is excellent in a balance among insulating properties, heat resistance, costs and the like. However, in order to comply with a demand for an enhancement of heat resistance accompanied with high-density mounting and multi-layer configuration of a printed wiring board in recent years, there is a limit in an increase of the heat resistance, inevitably. Furthermore, since the epoxy resin has a large coefficient of thermal expansion, it is attempted to reduce the thermal expansion by selecting an epoxy resin having an aromatic ring or filling an inorganic filler such as silica in a high density (see, for example, Patent Document 1).
  • In particular in recent years, in a package substrate for semiconductors, associated with miniaturization and thinning, a warpage resulting from a difference in the thermal expansion coefficient between a chip and a substrate is a large problem at the time of component mounting or package assembling. Therefore, it is required that the thermal expansion should be reduced. However, it is known that an increase of the filling amount of the inorganic filler causes a lowering of insulation reliability resulting from moisture absorption, an insufficient adhesive force between the resin composition layer and the wiring layer, and a failure of press molding.
  • Although a polybismaleimide resin which is widely used for high-density mounting or highly multi-layered laminate is very excellent in the heat resistance, it has high moisture absorption and a problem with the adhesion. Furthermore, as compared with an epoxy resin, the polybismaleimide resin requires a high temperature and a long time at the time of lamination, so that it has a drawback that the productivity is poor.
    That is, in the case of the epoxy resin, it can be generally cured at a temperature of 180 °C or less, whereas in the case of laminating the polybismaleimide resin, a long-term treatment at a high temperature of 220 °C or higher is required. Also, a modified imide resin composition is improved in moisture resistance and adhesion (see, for example, Patent Document 2); however, since it is modified with a low-molecular weight compound containing a hydroxyl group and an epoxy group for the purpose of ensuring solubility in commonly-used solvent such as methyl ethyl ketone, the resulting modified imide resin is significantly inferior in the heat resistance to the polybismaleimide resin.
    • [Prior Art Documents] [Patent Documents]
    • [Patent Document 1] JP-A-5-148343
    • [Patent Document 2] JP-A-6-263843
    [Summary of the Invention] [Problems to be solved by the Invention]
  • In view of the above existing circumstance, an object of the present invention is to provide a resin composition which is especially excellent in heat resistance and low thermal expansion properties, and a prepreg using the same, a laminate and a printed wiring board.
    • [Means for Solving the Problems]
  • In order to achieve the above object, the present inventors made extensive and intensive investigations. As a result, it has been found that a resin composition comprising a polybismaleimide resin and a silicone resin having a reactive organic group satisfies the above object.
  • That is, the present invention provides a resin composition, a prepreg, a laminate, and a printed wiring board as described below.
    1. (1) A resin composition comprising (a) a maleimide compound having at least two N-substituted maleimide groups in a molecular structure and (b) a silicone compound having at least one reactive organic group in a molecular structure;
    2. (2) The resin composition according to (1), further comprising (c) a thermosetting resin;
    3. (3) The resin composition according to (1) or (2), further comprising (d) an amine compound having an acidic substituent represented by the following general formula (I):
  • Figure imgb0001
  • wherein when a plurality of R1s are present, each R1 independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group as an acidic substituent; when a plurality of R2s are present, each R2 represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a halogen atom; x represents an integer of 1 to 5 and y represents an integer of 0 to 4, with the proviso that x + y = 5;
    (4) The resin composition according to any of (1) to (3), wherein the component (b) is a silicone compound containing a structure represented by the following general formula (II) :
  • Figure imgb0002
  • wherein each of R3 and R4 independently represents an alkyl group, a phenyl group, or a substituted phenyl group; and n represents an integer of 1 to 100;
    • (5) The resin composition according to any of (1) to (4), wherein the reactive organic group of the component (b) is at least one selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group;
    • (6) The resin composition according to any of (1) to (5), wherein the component (b) is a silicone compound having at least two reactive organic groups in a molecular structure;
    • (7) The resin composition according to any of (1) to (5), wherein the component (b) is a silicone compound having a reactive organic group on both ends;
    • (8) The resin composition according to any of (1) to (5), wherein the component (b) is a silicone compound having a reactive organic group on either end;
    • (9) The resin composition according to any of (1) to (5), wherein the component (b) is a silicone compound having a reactive organic group in the side chain;
    • (10) The resin composition according to any of (1) to (5), wherein the component (b) is a silicone compound having a reactive organic group in the side chain and on at least one end;
    • (11) The resin composition according to any of (1) to (10), wherein the component (c) is a thermosetting resin having an epoxy group and/or a cyanate group in a molecular structure;
    • (12) The resin composition according to any of (1) to (11), further comprising (e) a curing accelerator represented by the following formula (III) or (IV):
  • Figure imgb0003
  • wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and D represents an alkylene group or an aromatic hydrocarbon group,
  • Figure imgb0004
  • wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and B represents single bond or any one of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group;
    • (13) The resin composition according to any (1) to (12), further comprising (f) an inorganic filler;
    • (14) A prepreg using the resin composition according to any (1) to (13);
    • (15) A laminate obtained by laminating and molding the prepreg according to (14);
    • (16) A printed wiring board manufactured by using the laminate according to (15).
    [Effects of the Invention]
  • A prepreg obtained by impregnating or coating a substrate with a resin composition of the present invention, a laminate manufactured by laminating and molding the prepreg, and a multilayer printed wiring board manufactured by using the laminate are excellent in glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics, and are useful as a printed wiring boar for electronic devices.
    • [Modes for Carrying Out the Invention]
  • The present invention is described in detail below. The present invention is concerned with a resin composition comprising (a) a maleimide compound having at least two N-substituted maleimide groups in a molecular structure thereof and (b) a silicone compound having at least one reactive organic group in a molecular structure.
  • Examples of the maleimide compound having at least two N-substituted maleimide groups in a molecule as the component (a) in the resin composition of the present invention include N,N'-ethylenebismaleimide
    , N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidopenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluo ropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluo ropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2-bis(4-maleimidophenyl)disulfide, bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbe nzyl] benzene, 1,3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbe nzyl] benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbe nzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbe nzyl]benzene, and polyphenylmethane maleimide (for example, a trade name: BMI-2300, manufactured by Daiwa Fine Chemicals Co., Ltd., etc.). These maleimide compounds may be used alone or in combination with two or more thereof.
  • Among these maleimide compounds, bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, N,N'-(1,3-phenylene)bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, and polyphenylmethane maleimide are preferred from the viewpoint of high reactivity and higher heat resistance; and bis(4-maleimidophenyl)methane is especially preferred from the viewpoint of solubility in a solvent.
  • Examples of the silicone compound having at least one reactive organic group in a molecular structure as the component (B) include a silicone compound containing a structure represented by the following general formula (II):
  • Figure imgb0005
  • wherein each of R3 and R4 independently represents an alkyl group, a phenyl group, or a substituted phenyl group; and n represents an integer of 1 to 100.
  • A silicone compound having at least two reactive organic groups in a molecular structure is suitably used as the component (b) ; and a silicone compound having reactive organic groups on both ends of the above silicone structure, a silicone compound having a reactive organic group on either end, a silicone compound having a reactive organic group in the side chain, and a silicone compound having a reactive organic group in the side chain and on at least one end are used.
  • Examples of the reactive organic group in the silicone compound having at least one reactive organic group in a molecular structure of the component (B) include an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group.
    As the silicone compound having an epoxy group or epoxy groups in a molecular structure, commercially available products can be used. Examples thereof include products having epoxy groups on both ends, such as "X-22-163" (functional group equivalent weight: 200), "KF-105" (functional group equivalent weight: 490), "X-22-163A" (functional group equivalent weight: 1,000), "X-22-163B" (functional group equivalent weight: 1,750), and "X-22-163C" (functional group equivalent weight: 2,700); products having alicyclic epoxy groups on both ends, such as "X-22-169AS" (functional group equivalent weight: 500) and "X-22-169B" (functional group equivalent weight: 1,700); products having an epoxy group on either end, such as "X-22-1730X" (functional group equivalent weight 4,500); products having epoxy groups in the side chain and on both ends, such as "X-22-9002" (functional group equivalent weight: 5, 000) ; products having an epoxy group in the side chain, such as "X-22-343" (functional group equivalent weight: 525), "KF-101" (functional group equivalent weight: 350), "KF-1001" (functional group equivalent weight: 3,500), "X-22-2000" (functional group equivalent weight: 620), "X-22-4741" (functional group equivalent weight: 2,500), and "KF-1002" (functional group equivalent weight: 4,300); and products having an alicyclic epoxy group in the side chain, such as "X-22-2046" (functional group equivalent weight: 600) and "KF-102" (functional group equivalent weight: 3,600), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These can be used alone or in combination with two or more thereof, and furthermore, they can be used as a mixture with each epoxy resin.
    Among these silicone compounds having an epoxy group or epoxy groups in a molecular structure, "X-22-163A", "X-22-163B", "X-22-343", "X-22-9002", and "KF-101" are preferred from the viewpoint of heat resistance, "X-22-163A" and "X-22-163B" are more preferred; and "X-22-163B" is especially preferred from the viewpoint of low coefficient of thermal expansion.
  • As the silicone compound having an amino group or amino groups in a molecular structure, commercially available products can be used. Examples thereof include products having amino groups on both ends, such as "KF-8010" (functional group equivalent weight: 430), "X-22-161A" (functional group equivalent weight: 800), "X-22-161B" (functional group equivalent weight: 1,500), "KF-8012" (functional group equivalent weight: 2,200), "KF-8008" (functional group equivalent weight: 5,700), "X-22-9409" (functional group equivalent weight: 700), and "X-22-1660B-3" (functional group equivalent weight:2,200), all of which are manufactured by Shin-Etsu Chemical Co., Ltd., and "BY-16-853U" (functional group equivalent weight:460), "BY-16-853" (functional group equivalent weight: 650), and "BY-16-853B" (functional group equivalent weight: 2,200), all of which are manufactured by Dow Corning Toray Co., Ltd.; and products having an amino group in the side chain, such as "KF-868" (functional group equivalent weight: 8,800), "KF-865" (functional group equivalent weight: 5,000), "KF-864" (functional group equivalent weight: 3,800), "KF-880" (functional group equivalent weight: 1,800), and "KF-8004" (functional group equivalent weight: 1,500), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
    Among these silicone compounds having an amino group or amino groups in a molecular structure, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and BY-16-853B are preferred from the viewpoint of low coefficient of water absorption; and X-22-161A, X-22-161B, and KF-8012 are especially preferred from the viewpoint of low thermal expansion properties.
  • As the silicone compound having a hydroxyl group or hydroxyl groups in a molecular structure, commercially available products can be used. Examples thereof include products having hydroxyl groups on both ends, such as "KF-6001" (functional group equivalent weight: 900) and "KF-6002" (functional group equivalent weight: 1,600), all of which are manufactured by Shin-Etsu Chemical Co., Ltd.; products having phenolic hydroxyl groups on both ends, such as "X-22-1821" (functional group equivalent weight: 1,470), manufactured by Shin-Etsu Chemical Co., Ltd., and "BY-16-752A" (functional group equivalent weight: 1,500), manufactured by Dow Corning Toray Co., Ltd.; products having a hydroxyl group on either end, such as "X-22-170BX" (functional group equivalent weight: 2, 800) and "X-22-170DX" (functional group equivalent weight: 4,670), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. ; products having a hydroxyl group in the side chain, such as "X-22-4039" (functional group equivalent weight: 970) and "X-22-4015" (functional group equivalent weight: 1,870), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • As the silicone compound having a methacryl group or methacryl groups in a molecular structure, commercially available products can be used. Examples thereof include products having methacryl groups on both ends, such as "X-22-164A" (functional group equivalent weight: 860) and "X-22-164B" (functional group equivalent weight: 1,630); and products having a methacryl group on either end, such as "X-22-174DX" (functional group equivalent weight: 4,600), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • As the silicone compound having a mercapto group or mercapto groups in a molecular structure, commercially available products can be used. Examples thereof include products having mercapto groups on both ends, such as "X-22-167B" (functional group equivalent weight: 1,670); and products having a mercapto group in the side chain, such as "KF-2001" (functional group equivalent weight: 1,900) and "KF-2004" (functional group equivalent weight: 30,000), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination with two or more thereof.
  • As the silicone compound having a carboxyl group or carboxyl groups in a molecular structure, commercially available products can be used. Examples thereof include products having carboxyl groups on both ends, such as "X-22-162C" (functional group equivalent weight: 2,300); products having a carboxyl group on either end, such as "X-22-3710" (functional group equivalent weight: 1,450); and products having a carboxyl group in the side chain, such as "X-22-3701E" (functional group equivalent weight: 4,000), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or by mixing two or more thereof.
  • As the silicone compound having an alkoxy group or alkoxy groups in a molecular structure, commercially available products can be used. Examples thereof include products having an alkoxy group in the side chain, such as "FZ-3704" (functional group equivalent weight: 150), which is manufactured by Dow Corning Toray Co., Ltd. These may be used alone or by mixing two or more thereof.
  • The used amount of the component (b) is preferably 1 to 100 parts by mass, and more preferably 5 to 80 parts by mass based on 100 parts by mass of the component (a). When the used amount of the component (b) is 1 part by mass or more, it is possible to realize a low coefficient of thermal expansion. When the used amount of the component (b) is 100 parts by mass or less, adhesion to a copper foil and moldability can be ensured.
  • It is preferred that the resin composition of the present invention further comprises (c) a thermosetting resin. Although the thermosetting resin as the component (c) is not particularly limited, examples thereof include an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, and a melamine resin. These may be used alone or by mixing two or more thereof. Among them, an epoxy resin and a cyanate resin are preferred from the viewpoint of moldability and electric insulating properties.
  • Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, a bisphenol F novolac type epoxy resin, a stilbene type epoxy resin, a triazine skeleton-containing epoxy resin, a fluorene skeleton-containing epoxy resin, a triphenolphenolmethane type epoxy resin, a biphenyl type epoxy resin, a xylylene type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, a diglycidyl ether compound of a polyfunctional phenol compound or a polycyclic aromatic compound such as anthracene and a phosphorus-containing epoxy resin having a phosphorus compound introduced thereto. These may be used solely or in admixture of two or more kinds thereof. Among them, a biphenyl aralkyl type epoxy resin and a naphthalene type epoxy resin are preferred from the viewpoint of heat resistance and flame retardancy.
  • Examples of the cyanate resin include a bisphenol type cyanate resin such as a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate resin; and a prepolymer thereof which is partially converted into triazine. These may be used alone or by mixing two or more thereof. Among them, a novolac type cyanate resin is preferred from the viewpoint of heat resistance and flame retardancy.
  • The used amount of the component (c) is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass based on 100 parts by mass of the component (a). When the used amount of the component (c) is 10 parts by mass or more, more excellent moisture absorption characteristics and adhesion to a copper foil are obtained. When the used amount of the component (c) is 200 parts by mass or less, heat resistance can be ensured, and it is possible to realize a low coefficient of thermal expansion.
  • It is preferred that the resin composition of the present invention further comprises, as a component (d), an amine compound having an acidic substituent represented by the following general formula (I).
  • Figure imgb0006
  • wherein when a plurality of R1s are present, each R1 independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group as an acidic substituent; when a plurality of R2s are present, each R2 represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a halogen atom; x represents an integer of 1 to 5 and y represents an integer of 0 to 4, with the proviso that x + y = 5.
  • Examples of the amine compound as the component (d) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Among them, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of solubility and synthetic yield; and m-aminophenol and p-aminophenol are more preferred from the viewpoint of heat resistance.
  • The used amount of the component (d) is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass based on 100 parts by mass of the component (a). When the used amount of the component (d) is 0.1 parts by mass or more, more excellent heat resistance and adhesion to a copper foil are obtained. When the used amount of the component (d) is 20 parts by mass or less, heat resistance can be ensured.
  • It is preferred to allow the component (d) to react with the component (a) in advance. Although the organic solvent which is used for this reaction is not particularly limited, examples thereof include an alcohol based solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; an ether based solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene, and mesitylene; a nitrogen atom-containing solvent such as methylformamide, dimethylacetamide, and N-methylpyrrolidone; and a sulfur atom-containing solvent such as dimethyl sulfoxide. These can be used alone or by mixing two or more thereof. Among them, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferred from the viewpoint of solubility; cyclohexanone and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity; and propylene glycol monomethyl ether is especially preferred in view of the fact that it has a high volatility and hardly remains as a residual solvent at the time of manufacturing a prepreg.
  • Where necessary, a reaction catalyst for the above reaction may be used, and not particularly limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methyl imidazole and phenyl imidazole; and a phosphorus based catalyst such as triphenyl phosphine. These can be used alone or by mixing two or more thereof.
  • At the time of allowing the component (a) and the component (d) to react with each other in an organic solvent, a reaction temperature is preferably 70 to 150 °C, and more preferably 100 to 130 °C. A reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
  • For the purpose of enhancing heat resistance, flame retardancy, adhesion to a copper foil, and the like, it is desirable to use (e) a curing accelerator in the resin composition of the present invention, and examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines, a quaternary ammonium salt.
    Among them, imidazoles and derivatives thereof are preferred from the viewpoint of heat resistance, flame retardancy, adhesion to a copper foil, and the like. Furthermore, an isocyanate resin represented by the following general formula (III), or a compound substituted with a compound represented by the following general formula (IV), in which an imidazole group is substituted with an epoxy resin is more preferred because of excellent moldability at a relatively low temperature as not higher than 200 °C and excellent long-term stability of a varnish or a prepreg. Specifically, a compound represented by the following formula (V) or (VI) is especially preferred because it may be used in a small blending amount and is commercially inexpensive.
  • Figure imgb0007
  • wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and D represents an alkylene group or an aromatic hydrocarbon group.
  • Figure imgb0008
  • wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and B represents any one of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group.
  • Figure imgb0009
  • Figure imgb0010
  • The used amount of the curing accelerator (e) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and especially preferably 0.1 to 1 part by mass based on 100 parts by mass of the total amount of the components (a) to (d) in terms of solid content. When the used amount of the curing accelerator is 0.1 parts by mass or more, excellent heat resistance, flame retardancy and adhesion to a copper foil are obtained. When it is 10 parts by mass or less, the heat resistance, long-term stability and press moldability are not lowered.
  • The resin composition of the present invention may optionally comprise (f) an inorganic filler in combination. Examples of the inorganic filler include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, a glass powder of E-glass, T-glass, D-glass, etc., and a hollow glass bead. These can be used alone or by mixing two or more thereof.
  • Among these inorganic fillers as the component (f), silica is especially preferred from the viewpoint of dielectric characteristics, heat resistance, and low thermal expansion properties. Examples of the silica include precipitated silica which is manufactured by a wet process and has a high water content; and dry process silica which is manufactured by a dry process and does not substantially contain bonding water. Furthermore, the dry process silica includes crushed silica, fumed silica, and spherical fused silica depending on a difference of the manufacturing method. Among them, spherical fused silica is preferred from the viewpoint of low thermal expansion properties and high fluidity on being filled in the resin.
  • In the case of using spherical fused silica as the inorganic filler, its average particle size is preferably 0.1 to 10 µ m, and more preferably 0.3 to 8 µm. When the average particle size of the spherical fused silica is 0.1 µm or more, the fluidity on being highly-filled in the resin can be kept favorable. When it is 10 µm or less, an incorporation probability of coarse particles is reduced so as to suppress the generation of failure to be caused due to the coarse particles. The average particle size as referred to herein means a particle size which is read off the cumulative distribution curve at the 50% point, with the total volume of particles being 100%, and it can be measured by a laser diffraction-scattering type particle size distribution analyzer and so on.
  • A content of the inorganic filler (f) is preferably 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass based on 100 parts by mass of the total components (a) to (d) in terms of solid content. When the content of the inorganic filler falls within the range of 10 to 300 parts by mass based on 100 parts by mass of the total resin components, the moldability and low thermal expansion properties of the resin composition can be kept favorable.
  • In the present invention, known thermoplastic resin, elastomer, flame retarder and organic filler, and the like can be optionally used in combination so far as the object of the invention is adversely affected.
    Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, a polyphenylene ether resin, a phenoxy resin, a polycarbonate resin, a polyester resin, a polyamide resin, a polyimide resin, a xylene resin, a petroleum resin, and a silicone resin.
    Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.
    Examples of the organic filler include a silicone powder, an organic material powder of tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether and so on.
  • In the present invention, it is also possible to optionally add an ultraviolet ray absorber, an antioxidant, a photopolymerization initiator, a fluorescent brightener, an adhesion improver, etc., and there are no particular limitations. Examples thereof include an ultraviolet ray absorber such as a benzotriazole based material; an antioxidant such as a hindered phenol antioxidant and styrenated phenol; a photopolymerization initiator such as benzophenones, benzyl ketals, and thioxanthone-based type; a fluorescent brightener such as a stilbene derivative; and an adhesion improver such as a urea compound such as urea silane and a silane coupling agent
    The resin composition of the present invention is used as a varnish at the time of manufacturing a prepreg. The solvent which is used for varnish is the same as the solvent which is used for the above reaction. It is preferred to use the varnish in a solid content concentration of 50 to 75 % by mass.
  • The prepreg of the present invention is obtained by impregnating or coating a substrate with the above-described resin composition of the present invention. The prepreg of the present invention is described in detail below.
    The prepreg of the present invention can be manufactured by impregnating or coating a substrate with the resin composition of the present invention, followed by semi-curing (B-staging) by heating for example. As the substrate herein, well-known materials which are used for various laminates for electrical insulating materials can be used. Examples of the material include fibers of an inorganic material such as E-glass, D-glass, S-glass, and Q-glass; fibers of an organic material such as polyimide, polyester, and polytetrafluoroethylene; and mixtures thereof.
  • Although such a substrate has a form, such as a woven fabric, a unwoven fabric, a roving, a chopped strand mat, and a surfacing mat, the material and the shape are selected depending on an application or a performance of the target molded article, and the material and the shape can be employed alone or in combination with two or more thereof, where necessary. Although the substrate is not particularly limited with respect to its thickness, for example, those having a thickness of about 0.03 to 0.5 mm can be used. Those having been subjected to a surface treatment with a silane coupling agent, etc., or those having been subjected to a mechanical opening treatment are suitable from the vierpoint of heat resistance, moisture resistance, and processability.
  • The prepreg of the present invention can be obtained by impregnating or coating the substrate with the resin composition in such a manner that an adhesion amount thereof to the substrate is 20 to 90 % by mass in terms of a resin content of the prepreg after drying, and then heating for drying usually at a temperature of 100 to 200 °C for 1 to 30 minutes to achieve semi-curing (B-staging).
  • The laminate plate of the present invention can be formed by laminating and molding the above prepreg of the present invention. The laminate can be, for example, manufactured by such that 1 to 20 sheets of the prepreg of the present invention are superimposed, and a metal foil such as copper and aluminum is disposed on one surface or both surfaces thereof. The metal foil is not particularly limited so far as it is used for an application of electrical insulating materials.
    As for a molding condition, for example, methods for a laminate and a multilayered board for electrical insulating material can be applied. The molding can be performed within the temperature range of 100 to 250 °C under a pressure of 0.2 to 10 MPa for a heating time of 0.1 to 5 hours by using a multiplaten press, a multiplaten vacuum press, a continuous molding machine, or an autoclave molding machine, for example. In addition, a laminate can be manufactured by combining the prepreg of the present invention with a wiring board for inner layer and laminating and molding the combination.
  • The printed wiring board of the present invention is manufactured by forming a circuit on the surface of the laminate. That is, a conductor layer of the laminate according to the present invention is subjected to wiring processing by a usual etching method, and a plurality of the laminates having been subjected to wiring processing are laminated via the above prepreg and then subjected to heat press processing, thereby achieving multilayering in block. Thereafter, a multilayered printed wiring board can be manufactured through the formation of a through-hole or a blind via hole by means of drill processing or laser processing and the formation of an interlayer connection by plating or with an electrically conductive paste.
    • [Examples]
  • The present invention is described in more detail with reference to the following Examples, but should not be restricted at all.
    It should be noted that laminates obtained in the respective Examples and Comparative Examples were used and measured and evaluated with respect to glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics in the following methods.
    1. (1) Measurement of glass transition temperature (Tg):
      • A substrate for evaluation of 5 mm square was fabricated by dipping a copper clad laminate in a copper etching liquid to remove a copper foil and subjected to thermal mechanical analysis by a compression method using a TMA test apparatus (TMA2940, manufactured by Du Pont). The substrate for evaluation was installed in the apparatus in the Z-direction and then continuously measured twice under a measurement condition at a load of 5 g and at a heating rate of 10 °C/min. Tg expressed by a point of intersection of different tangents of a thermal expansion curve in the second measurement was determined and evaluated for heat resistance.
    2. (2) Measurement of coefficient of thermal expansion:
      • A substrate for evaluation of 5 mm square was fabricated by dipping a copper clad laminate in a copper etching liquid to remove a copper foil and subjected to thermal mechanical
    analysis by a compression method using a TMA test apparatus (TMA2940, manufactured by Du Pont). The substrate for evaluation was installed in the apparatus in the X-direction and then continuously measured twice under a measurement condition at a load of 5 g and at a heating rate of 10 °C/min. An average coefficient of thermal expansion at 30 °C to 100 °C in the second measurement was calculated, and this was defined as a value of the coefficient of thermal expansion.
    • (3) Evaluation of solder heat resistance:
      • A copper clad laminate having a size of 5 cm square was fabricated, the substrate for evaluation was floated in a soldering bath at a temperature of 288 °C for one minute, and then an appearance thereof was observed to evaluate the solder heat resistance.
    • (4) Evaluation of warpage amount:
      • A warpage amount of a substrate was evaluated by means of shadow moire analysis using TherMoire PS200, manufactured by AKROMETRIX. A sample size of the substrate was set to 40 mm x 40 mm, and a measuring area was set to 36 mm x 36 mm. The sample was heated from room temperature to 260 °C and then cooled to 50 °C, thereby measuring the warpage amount.
    Examples 1 to 18 and Comparative Examples 1 to 3
  • Components (a) to (d), (e) a curing accelerator, and (f) an inorganic filler as shown below were mixed in a blending proportion (parts by mass) shown in each of Tables 1 to 5, and methyl ethyl ketone is used as a dilution solvent, thereby obtaining a homogenous varnish having a resin content of 65 % by mass.
    Subsequently, the above varnish was applied onto an E-glass cloth having a thickness of 0.1 mm, and heat-dried at 160 °C for 10 minutes, thereby obtaining a prepreg having a resin content of 50% by mass.
    Four sheets of this prepreg were superimposed, and an 18 µm-thick electrolytic copper foil was disposed on the top and bottom, followed by pressing under a pressure of 2.5 MPa at a temperature of 230 °C for 90 minutes, thereby obtaining a copper clad laminate.
    The measurement and evaluation results of the obtained copper clad laminates are shown in Tables 1 to 5.
    • (a) Maleimide compound:
      • Bis(4-maleimidophenyl)methane
      • 3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethanebismalei mide
    • (b) Silicone compound:
      • X-22-161A (duel-end type of amino-modified silicone, functional group equivalent weight: 800, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-161B (duel-end type of amino-modified silicone, functional group equivalent weight: 1,500, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • KF-8012 (duel-end type of amino-modified silicone, functional group equivalent weight: 2,200, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • KF-864 (single-end type of amino-modified silicone, functional group equivalent weight: 3,800, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-163B (duel-end type of epoxy-modified silicone, functional group equivalent weight: 1,750, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • KF-6002 (duel-end type of hydroxyl-modified silicone, functional group equivalent weight: 1,600, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-1821 (duel-end type of phenolic hydroxyl-modified silicone, functional group equivalent weight: 1,470, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-164A (duel-end type of methacryl-modified silicone, functional group equivalent weight: 860, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-167B (duel-end type of mercapto-modified silicone, functional group equivalent weight: 1,670, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • X-22-162C (duel-end type of carboxyl-modified silicone, functional group equivalent weight: 2,300, manufactured by Shin-Etsu Chemical Co., Ltd.)
      • FZ-3704 (side-chain type of alkoxy-modified silicone, functional group equivalent weight: 150, manufactured by Dow Corning Toray Co., Ltd.)
    • (c) Thermosetting resin:
      • Biphenyl aralkyl type epoxy resin (NC-3000, manufactured by Nippon Kayaku Co., Ltd.)
      • Bisphenol A type cyanate resin (B10, manufactured by Lonza Japan Ltd.)
    • (d) Amine compound:
      • m-Aminophenol
        p-Aminophenol
    • (e) Curing accelerator:
      • G-8,009L (an adduct of hexamethylene diisocyanate resin and 2-ethyl-4-methyl imidazole, which is the compound represented by the above formula (V))
    • (f) Inorganic filler: Fused silica (SO-C2, manufactured by Admatechs Company Limited)
    Other compounds:
    • Diaminodiphenylmethane (comparative example)
    • 2,2-Bis[4-(aminophenoxy)phenyl]propane (comparative example)
  • Table 1
    Example 1 Example 2 Example 3 Example 4 Example 5
    Thermosetting composition (parts by mass)
    (a) Maleimide compound
    Bis(4-maleimidophenyl)methane 40 40 40 40 40
    3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide
    (b) Silicone compound
    X-22-161A 15 15
    X-22-161B 15 15
    KF-8012 15
    (c) Thermosetting resin
    Biphenyl aralkyl type epoxy resin 40 40 40 40 40
    Bisphenol A type cyanate resin
    (d) Amine compound
    m-Aminophenol 5 5 5
    p-Aminophenol 5 5
    Curing accelerator
    G-8009L 0.5 0.5 0.5 0.5 0.5
    (e) Inorganic filler
    Fused silica 50 50 50 50 50
    Performances of laminate
    (1) Glass transition temperature (°C) 260 260 265 260 265
    (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.5 9.0 8.5 9.0
    (3) Solder dip resistance good good good good good
    (4) Warpage amount (µm) 50 45 45 40 45
  • Table 2
    Example 6 Example 7 Example 8 Example 9 Example 10
    Thermosetting composition (parts by mass)
    (a) Maleimide compound
    Bis(4-maleimidophenyl)methane 40 40 40 40
    3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide 40
    (b) Silicone compound
    X-22-161A 15 15 15
    X-22-161B 15 15
    KF-8012
    (c) Thermosetting resin
    Biphenyl aralkyl type epoxy resin
    Bisphenol A type cyanate resin 40 40 40 40 40
    (d) Amine compound
    m-Aminophenol 5 5 5
    p-Aminophenol 5 5
    Curing accelerator
    G-8009L 0.5 0.5 0.5 0.5 0.5
    (e) Inorganic filler
    Fused silica 50 50 50 50 50
    Performances of laminate
    (1) Glass transition temperature (°C) 250 250 250 250 255
    (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.0 8.5 8.0 8.5
    (3) Solder dip resistance good good good good good
    (4) Warpage amount (µm) 45 40 40 45 45
  • Table 3
    Example 11 Example 12 Example 13 Example 14 Example 15
    Thermosetting composition (parts by mass)
    (a) Maleimide compound
    Bis(4-maleimidophenyl)methane 40 40 40 40 40
    3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide
    (b) Silicone compound
    KF-864 15
    X-22-163B 15
    KF-6002 15
    X-22-1821 15
    X-22-164A 15
    (c) Thermosetting resin
    Biphenyl aralkyl type epoxy resin
    Bisphenol A type cyanate resin 40 40 40 40 40
    (d) Amine compound
    m-Aminophenol
    p-Aminophenol 5 5 5 5 5
    Curing accelerator
    G-8009L 0.5 0.5 0.5 0.5 0.5
    (e) Inorganic filler
    Fused silica 50 50 50 50 50
    Performances of laminate
    (1) Glass transition temperature (°C) 260 260 260 260 260
    (2) Coefficient of thermal expansion (ppm/°C) 8.5 8.0 8.5 8.0 8.5
    (3) Solder dip resistance good good good good good
    (4) Warpage amount (µm) 45 45 40 40 45
  • Table 4
    Example 16 Example 17 Example 18
    Thermosetting composition (parts by mass)
    (a) Maleimide compound
    Bis(4-maleimidophenyl)methane 40 40 40
    3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide
    (b) Silicone compound
    X-22-167B 15
    X-22-162C 15
    FZ-3704 15
    (c) Thermosetting resin
    Biphenyl aralkyl type epoxy resin
    Bisphenol A type cyanate resin 40 40 40
    (d) Amine compound
    m-Aminophenol
    p-Aminophenol 5 5 5
    Curing accelerator
    G-8009L 0.5 0.5 0.5
    (e) Inorganic filler
    Fused silica 50 50 50
    Performances of laminate
    (1) Glass transition temperature (°C) 260 260 260
    (2) Coefficient of thermal expansion (ppm/°C) 8.0 8.5 9.5
    (3) Solder dip resistance good good good
    (4) Warpage amount (µm) 45 40 50
  • Table 5
    Comparative Example 1 Comparative Example 2 Comparative Example 3
    Thermosetting composition (parts by mass)
    (a) Maleimide compound
    Bis(4-maleimidophenyl)methane 40 40
    3,3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide 40
    (b') Other compound
    Diaminodiphenylmethane 15
    2,2-Bis[4-(aminophenoxy)phenyl]propane 15 15
    (c) Thermosetting resin
    Biphenyl aralkyl type epoxy resin
    Bisphenol A type cyanate resin 40 40 40
    (d) Amine compound
    m-Aminophenol 5 5
    p-Aminophenol 5
    Curing accelerator
    G-8009L 0.5 0.5 0.5
    (e) Inorganic filler
    Fused silica 50 50 50
    Performances of laminate
    (1) Glass transition temperature (°C) 260 255 255
    (2) Coefficient of thermal expansion (ppm/°C) 11.0 10.5 11.0
    (3) Solder dip resistance good good good
    (4) Warpage amount (µm) 75 55 55
  • As is clear from Tables 1 to 5, the Examples of the present invention are excellent in the glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics. On the other hand, the Comparative Examples are inferior in any one of the glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics to the Examples.
    • [Industrial Applicability]
  • A multi-layered printed wiring board manufactured by using a laminate which is manufactured by laminating and molding a prepreg obtained from the thermosetting resin composition of the present invention is excellent in glass transition temperature, coefficient of thermal expansion, solder dip resistance, and warpage characteristics, and is useful as a highly integrated printed wiring board for electronic devices.

Claims (16)

  1. A resin composition comprising (a) a maleimide compound having at least two N-substituted maleimide groups in a molecular structure and (b) a silicone compound having at least one reactive organic group in a molecular structure.
  2. The resin composition according to claim 1, further comprising (c) a thermosetting resin.
  3. The resin composition according to claim 1 or 2, further comprising (d) an amine compound having an acidic substituent represented by general formula (I):
    Figure imgb0011
     when a plurality of R1s are present, each R1 independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group as an acidic substituent; when a plurality of R2s are present, each R2 represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a halogen atom; x represents an integer of 1 to 5 and y represents an integer of 0 to 4, with the proviso that x + y = 5.
  4. The resin composition according to any of claims 1 to 3, wherein the component (b) is a silicone compound containing a structure represented by general formula (II):
    Figure imgb0012
     wherein each of R3 and R4 independently represents an alkyl group, a phenyl group, or a substituted phenyl group; and n represents an integer of 1 to 100.
  5. The resin composition according to any of claims 1 to 4, wherein the reactive organic group of the component (b) is at least one selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group.
  6. The resin composition according to any of claims 1 to 5, wherein the component (b) is a silicone compound having at least two reactive organic groups in a molecular structure.
  7. The resin composition according to any of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group on both ends.
  8. The resin composition according to any of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group on either end.
  9. The resin composition according to any of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group in the side chain.
  10. The resin composition according to any of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group in the side chain and on at least one end.
  11. The resin composition according to any of claims 1 to 10, wherein the component (c) is a thermosetting resin having an epoxy group and/or a cyanate group in a molecular structure.
  12. The resin composition according to any of claims 1 to 11, further comprising (e) a curing accelerator represented by formula (III) or (IV):
    Figure imgb0013
     wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and D represents an alkylene group or an aromatic hydrocarbon group; and
    Figure imgb0014
     wherein each of R6, R7, R8, and R9 independently represents a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 5, or a phenyl group; and B represents single bond or any one of an alkylene group, an alkylidene group, an ether group, and a sulfonyl group.
  13. The resin composition according to any of claims 1 to 12, further comprising (f) an inorganic filler.
  14. A prepreg using the resin composition according to any of claims 1 to 13.
  15. A laminate plate obtained by laminating and molding the prepreg according to claim 14.
  16. A printed wiring board manufactured by using the laminate according to claim 15.
EP12736878.5A 2011-01-18 2012-01-17 Resin composition, and printed wiring board, laminated sheet, and prepreg using same Withdrawn EP2666825A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9902851B2 (en) 2012-10-19 2018-02-27 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, laminate, and printed wiring board
EP3467028A4 (en) * 2016-05-31 2020-03-04 Mitsubishi Gas Chemical Company, Inc. Resin composition, laminate, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device
EP3909758A4 (en) * 2019-01-11 2022-09-28 Daikin Industries, Ltd. Fluororesin composition, fluororesin sheet, multilayer body and substrate for circuits
WO2024131943A1 (en) * 2022-12-23 2024-06-27 广东生益科技股份有限公司 Resin composition and use thereof

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101832869B1 (en) * 2011-01-18 2018-04-13 히타치가세이가부시끼가이샤 Resin composition, and printed wiring board, laminated sheet, and prepreg using same
JP6107050B2 (en) * 2012-10-26 2017-04-05 日立化成株式会社 Thermosetting resin composition, prepreg, laminate and printed wiring board
JP6357762B2 (en) * 2012-11-28 2018-07-18 日立化成株式会社 Modified siloxane compound, thermosetting resin composition, prepreg, film with resin, laminate, multilayer printed wiring board and semiconductor package
JP6167850B2 (en) * 2013-10-29 2017-07-26 日立化成株式会社 Thermosetting resin composition, prepreg using the same, film with resin, laminate, printed wiring board, and semiconductor package
JP6229439B2 (en) * 2013-11-05 2017-11-15 住友ベークライト株式会社 Metal-clad laminate, printed wiring board, and semiconductor device
JP6476599B2 (en) * 2014-06-09 2019-03-06 日立化成株式会社 Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same
JP2015232066A (en) * 2014-06-09 2015-12-24 日立化成株式会社 Thermosetting resin composition, and prepreg, laminate and printed wiring board prepared using the same
JP6596811B2 (en) * 2014-07-25 2019-10-30 日立化成株式会社 Thermosetting resin composition, prepreg using the same, film with resin, laminated board, multilayer printed wiring board, and semiconductor package
JP6428082B2 (en) * 2014-09-16 2018-11-28 日立化成株式会社 Thermosetting resin composition, prepreg, laminate and printed wiring board
JP2016079317A (en) * 2014-10-20 2016-05-16 日立化成株式会社 Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same
JP2018531317A (en) * 2015-08-08 2018-10-25 デジグナー モレキュールズ インク． Anionic curable composition
JP6785422B2 (en) * 2015-12-22 2020-11-18 昭和電工マテリアルズ株式会社 Thermosetting resin composition, prepreg, film with resin, laminated board, multilayer printed wiring board and semiconductor package
JP6686433B2 (en) * 2015-12-28 2020-04-22 日立化成株式会社 Underfill resin composition, electronic component device, and method for manufacturing electronic component device
JP6924388B2 (en) * 2016-05-02 2021-08-25 三菱瓦斯化学株式会社 Resin composition, prepreg, resin sheet, laminated resin sheet, laminated board, metal foil-clad laminated board, and printed wiring board
JP2018016796A (en) * 2016-07-19 2018-02-01 セントラル硝子株式会社 Curable resin composition and cured product of the same, and semiconductor device using them
WO2018016405A1 (en) * 2016-07-19 2018-01-25 セントラル硝子株式会社 Curable resin composition, cured product of same, and semiconductor device using said cured product
CN110662793B (en) 2017-03-28 2022-05-10 昭和电工材料株式会社 Prepreg for coreless substrate, and semiconductor package
JP6597721B2 (en) * 2017-06-28 2019-10-30 日立化成株式会社 Thermosetting resin composition, prepreg using the same, film with resin, laminate, printed wiring board, and semiconductor package
JP6988204B2 (en) * 2017-06-29 2022-01-05 昭和電工マテリアルズ株式会社 Thermosetting resin composition, prepreg, laminated board, printed wiring board and high-speed communication compatible module
CN109054381B (en) * 2018-07-06 2020-09-11 苏州生益科技有限公司 Modified maleimide resin composition, prepreg and laminated board prepared from same
JP7024672B2 (en) * 2018-09-12 2022-02-24 信越化学工業株式会社 Thermosetting resin composition, thermosetting resin film and semiconductor device
JP7365574B2 (en) * 2019-07-29 2023-10-20 三菱瓦斯化学株式会社 Maleimide compounds and their production methods, amic acid compounds and their production methods, resin compositions, cured products, resin sheets, prepregs, metal foil clad laminates, printed wiring boards, sealing materials, fiber reinforced composite materials, adhesives, and semiconductor devices
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CN114230793B (en) * 2021-12-30 2024-03-29 苏州生益科技有限公司 Modified bismaleimide prepolymer and preparation method and application thereof
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CN116804116B (en) * 2022-12-15 2024-10-01 广东生益科技股份有限公司 Prepreg and application thereof

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4847154A (en) * 1987-05-29 1989-07-11 Basf Corporation Thermosetting resin systems containing secondary amine-terminated siloxane modifiers
JPH03221526A (en) * 1990-01-26 1991-09-30 Hitachi Chem Co Ltd Production of cured product of maleimide resin
JPH05186661A (en) * 1991-10-24 1993-07-27 Nippon Soda Co Ltd Curable resin composition
JP2740990B2 (en) 1991-11-26 1998-04-15 株式会社日立製作所 Low thermal expansion resin composition for pressure molding
JPH06122765A (en) * 1992-09-02 1994-05-06 Mitsubishi Kasei Corp Resin composition for semiconductor sealing
JPH06145380A (en) * 1992-11-13 1994-05-24 Nec Corp Prepreg and copper-clad laminate
JP3372982B2 (en) 1993-03-12 2003-02-04 三井化学株式会社 Thermosetting resin composition and prepreg and laminate using the same
JPH11124487A (en) * 1997-10-22 1999-05-11 Mitsubishi Gas Chem Co Inc Cyanic acid ester-maleimide liquid resin composition and sealed semiconductor device
JP4140115B2 (en) * 1999-02-16 2008-08-27 東亞合成株式会社 Curable composition
JP2000323804A (en) * 1999-05-07 2000-11-24 Toagosei Co Ltd Copper clad laminate plate for printed wiring board
JP2002121520A (en) * 2000-10-05 2002-04-26 Saehan Ind Inc Adhesive tape for electronic part
JP4957166B2 (en) * 2005-10-14 2012-06-20 三菱瓦斯化学株式会社 Prepreg and copper clad laminate
JP5176068B2 (en) * 2006-10-24 2013-04-03 日立化成株式会社 Conductor-clad laminate, printed wiring board and multilayer wiring board
JP2008095014A (en) * 2006-10-13 2008-04-24 Tomoegawa Paper Co Ltd Thermosetting resin composition for qfn(quad flat non-lead) and adhesive sheet
JP5417799B2 (en) * 2008-10-30 2014-02-19 日立化成株式会社 Thermosetting resin composition, and prepreg and laminate using the same
JP5149823B2 (en) * 2009-01-27 2013-02-20 京セラケミカル株式会社 Heat resistant resin composition and molded product using the same
CN102365310B (en) * 2009-03-27 2013-11-20 日立化成工业株式会社 Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same
JP5589292B2 (en) * 2009-03-27 2014-09-17 日立化成株式会社 Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same
JP5149917B2 (en) * 2009-03-27 2013-02-20 日立化成工業株式会社 Thermosetting resin composition, and prepreg, laminate and multilayer printed wiring board using the same
KR101832869B1 (en) * 2011-01-18 2018-04-13 히타치가세이가부시끼가이샤 Resin composition, and printed wiring board, laminated sheet, and prepreg using same
JP6122765B2 (en) * 2013-11-01 2017-04-26 日立建機株式会社 Work machine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012099132A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9902851B2 (en) 2012-10-19 2018-02-27 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, laminate, and printed wiring board
EP3467028A4 (en) * 2016-05-31 2020-03-04 Mitsubishi Gas Chemical Company, Inc. Resin composition, laminate, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device
US11053382B2 (en) 2016-05-31 2021-07-06 Mitsubishi Gas Chemical Company, Inc. Resin composition, laminate, semiconductor wafer with resin composition layer, substrate for mounting semiconductor with resin composition layer, and semiconductor device
EP3909758A4 (en) * 2019-01-11 2022-09-28 Daikin Industries, Ltd. Fluororesin composition, fluororesin sheet, multilayer body and substrate for circuits
US11963297B2 (en) 2019-01-11 2024-04-16 Daikin Industries, Ltd. Fluororesin composition, fluororesin sheet, laminate and substrate for circuits
WO2024131943A1 (en) * 2022-12-23 2024-06-27 广东生益科技股份有限公司 Resin composition and use thereof

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CN105602197B (en) 2020-11-20
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CN103328577A (en) 2013-09-25
CN105504809A (en) 2016-04-20
JP6333791B2 (en) 2018-05-30
TW201605921A (en) 2016-02-16
TW201249885A (en) 2012-12-16
TWI602843B (en) 2017-10-21
JP2018028105A (en) 2018-02-22
WO2012099132A1 (en) 2012-07-26
JP6241536B2 (en) 2017-12-06
JP2016028163A (en) 2016-02-25
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CN105462253A (en) 2016-04-06
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TWI541263B (en) 2016-07-11
KR101832869B1 (en) 2018-04-13

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